Process for polymerization of propylene



@pm m5 M4.. E. v. MEE

PROCESS FOR POLYMERIZTION OF PROPYLENE l Filed Sept. 2. 19M

CA m w mm...

UNITED- STATES PATENT PROCESS FOR POLYMERIZATION F PROPYLENE Eugene V. Kleber, Wyandotte, Mich., assignor to Sharples Chemicals Inc., Philadelphia, Pa., a corporation of Delaware Application September 2, 1944, Serial No. 552,493

GFFICE The present invention pertains to dimerization of open chain olefinie hydrocarbons containing between three and six carbon atoms. A feature of the invention consists in the fact that it provides a, method by which the starting material 5 to convert more than 10% of the olen to the may be converted to the desired dimer in Very rrespl'tlmgmg 9'(lmeg ddming any Single PaSS hi h 1e1d roug t ecat st e gIhalinvention was perfected in connection with By maintaining a relatively short period o f experimental work involving research to convert contact between any particular portion of the propylene into a mixture of hexenes, and it will l0 propylene under treatment and the catalyst duraccordingly be described with reference to such ing any given pass through the catalyst, the fora process, with the understanding that analogous mation ofproducts of higher degree of polymeriprocedure may be adopted in conversion of other zation than the dimer is almost completely avoidolens Within the range indicated to their died. Thus, by operating under super-atmospher.. mers within the scope of the invention, as dened l5 iii rressu artid efecltingfcontact or liquid phase in the attached claims. o e n wi t e cata yst or a time long enough A number of problems are enlunteledrn et to convert -a substantial part of the olefin into` tem ts to dmerize propylene w ich are c aracthe corresponding dimer but suiciently short terisltic of the problems. encountered in attempted substantially to avoid higherdegrees ofpolymeridimerization of the other starting materials or zation, and by re-boiling unpolymerized propylmixtures or the invention. Clalysts dwhich ene to subject it repeatedly te contact with the iause ditxerz'ationwa ttlsrifglllalelggrnfsg pol'meizaion catalysthe volumet dof propylexe on of e imer un er rea men mayconver e very large y form higher pelymel's- The dimers tend t0 de" to the desired dimer. In view of the higher boilpolymerize in lthe preslnce oflttl attlyst t0 25 ing point of the dimer, the process may be conform monomers, With t e xeSll a ere a ducted in such a manner as to avoid contact of tendency to establish an equilibrium at W1 11Ch this dimer with the catalyst after the dimer has the mixture contlains montomer, dnler 11d Tlig' once been formed and returned to the lbody of er olymers. T e presen mven 0n Par c 1i uid under treatmen 19111; Vadvantageous in that it Provides a .Pmcess qrIhe process may betmore clearly understood by by Which dimeriza'tlon can be effected Wlth for' reference to the attached ow sheet, in which, mation of only a Small quantity 0f higher Poly the single figure illustrates in schematic form an mers end by which. by Continued praelce 0f the apparatus designed for production of hexylene dimerization process, practically all of the origifrom pr0py1ene nal starting materia1 can be converted into the 35 Referring to the now sheet by reference cham desired dimer. acters, the apparatus comprises a still l0 in which Starting wlth pl0pylenef0r example'i'he mitin a body of propylene under treatment may be body of the material under treatment 1S mam' maintained under super-atmospheric pressure in tained in liquid Phase under Super`atmosphelic the liquid phase The still is surrounded b pressure in a still. Heat is applied to the liquld 40 jacket thmu'ghwhich stea th hy to eiect vaporization of a part thereof, and the exchangeuid may be ap Hedrr; Offro teli; lea vaporized portion is condensed to re-form the of the propylene Upon alaplcaol gc; heitir nquid. This liquid then flows by gravity through the stm lo prOpylene vapors ascend to the a chamber containing a bed of solid llolymerlzaf r packed column Iz which may contain la deph1eg tion catalyst and returns through this bed o 4.,

n to meh heat mator I3. The ascending vapors pass through catalyst to the body of liquid ole w condu1t I4 at the top of the column into con- 1s being applied to effect continued vaporization. v

In the practice of the invention as described deliser I5 which may conta'm a dephlegmator 's above the volume of the bed of catalyst is main- Whlch causes Condensatio@ 0f the propylene Va" tained suiiciently small with respect to the quan- Dors-t The Condensed hquld descends t0 3f bed my of uquid being perconred through it `.errer 0f Ca alyst "y Whlch may. be any Solid Catalyst condensation to provide a very short period 0f of type capable of nducmg polymef'lzation re' Contact between the percolatmg liquid and the actions to take place. After a brief passage solid body ofI catalyst. A contact time of the through the catalyst bed Il, the mixture of dimer and unpolymerzed monomer descends order of magnitude of between one and twenty 1 Claim. (Cl. 26o-683.15)

secondsv will usually be sumcient. In any case, the process is practiced in such a manner that the length of time of contact between the catalyst and the olen under treatment is insuilicient 3 through conduit I8 and is thus returned to the body of liquid in the still I 0.

It will be seen from the above description that the propylene of the mixture returned through conduit I8 to the still I0 may continue to be passed indefinitely through the steps of the cycle described above, and thus continually subjected to contact with the polymerization catalyst until substantially all.of this propylene has been dimerized. With respect to the hexylene formed in any given pass, on the other hand, this material remains in the still I0, or is returned prompt- =ly to that still by the condensing eect of the packing in column I2 or by the plates I3, in case it is again vaporized. We thus have repeated contact of propylene With the catalyst, until the propylene is ultimately dimerized, but the process is practiced in such a manner as to prevent further contact of the formed hexylene with the catalyst, and further condensation of this hexylene with hexylene or propylene in contact with the catalyst is prevented after the hexylene has once been returned to the still.

Best results in practice oi' the invention have been attained by heating the reaction mixture so vigorously as to create a pressure condition involving pressures very close to the critical pressure of the oleiln material to be converted to the dimer. This entails, of course, use of temperatures which are suiiciently close to the critical temperatures to cause continued ebullition of the olefin monomer` under the pressures attained. In general, best results have been attained in operations in which temperatures within C. of the critical temperature of the olefin under treatment are used. Thus, in dimerization of the propylene, it is best to operate between a temperature of 81.4 C. and 91.4 C., and the dimerization of other olens between 3 and 6 carbon atoms can also best be attained at temperatures Within 10 C. of the critical temperature. When pentene-2 is treated, the preferred temperature is between 192 and 202 C. although lower temperatures may be used.

While I have chosen to describe the invention specifically with reference to treatment of propylene, and the invention was originally conceived with reference to dimerization of this material, it may also 'be practiced in treatment of the various other olens within the carbon content limits discussed above. Thus, 'the Various butylenes, amylenes and hexylenes, including isomeric mixtures of these materials, may be treated in a manner similar to that described above with reference to propylene to produce the corresponding dimers.

The only physical limitations on the catalysts to be used in practice of the invention are that they must be solids and insoluble to any substantial extent in the liquids being percolated through them. This last-mentioned qualification results from the fact that, if the catalyst were to be dissolved to a substantial extent in the liquid under treatment, it would gradually be washed down into the still containing the liquid material under treatment. The presence of the catalyst in this still together with the mixture of dimers and monomers would ultimately result in further polymerization to defeat the object of the invention.

It is impossible to specify with exactness general instructions either as to the contact time or temperature by which best conversions and yields can be attained in practice of the invention, for these factors depend upon the particular catalyst being used and the particular olen being dimerized. With less active catalysts, the apparatus should be arranged to provide a. longer contact time at any given temperature, or a higher temperature should be employed, as will be obvious to any skilled chemist. Excellent results have been attained in practice of the invention by use of active clay catalysts containing a high proportion of aluminum silicate (e. g. tonsil, Florida. earth, Retrol, Filtrol, etc. clays), but the invention is by no means restricted to use of such catalysts, since any one of the many solid polymerization catalysts known to the art and having the above-discussed characteristics may be employed. Thus, for example, a suitably supported Friedel-Crafts catalyst may be used to catalyze the reaction.

Example I Twenty-eight pounds of propylene were charged into an apparatus constructed as illustrated in the attached flow sheet. Steam was applied to the jacket II and the propylene was vaporized into the column I2, which was packed with Raschig rings. A small reflux was maintained in the dephlegmator I3 to prevent polymer from rising through the column. Pure propylene passed through pipe I4 and condensed on the dephlegmator I6 and fell through the catalyst II at the rate of 183 pounds per hour. The catalyst consisted of one liter of Kleeno granular activated clay. The steam pressure in the jacket II and the cooling water rates in the dephlegmators I3 and I6 were so adjusted that the pressure was maintained at 570 pounds per square inch (gauge). At this pressure the temperature of the propylene entering the catalyst chamber was 84 C. After 11.5 hours of such operation, the polymerized material in the still pot I0 was Withdrawn. The polymer was found to contain 4.85 pounds of dimer and 3.20 pounds of higher polymer. Fourteen percent by volume of the dimer was found to be tetramethylethylene.

Example II Seventeen and one-quarter pounds of pentene-2 were charged into still pot I0 and were boiledthrough column I2 by the application of steam to the jacket II. Pure pentene-2 vapor, passed through pipe I 4 into the reactor I5, condensed on the dephlegmator I6 and fell on the catalyst I1. The catalyst was two liters of granular Kleenfio activated clay. The pipe I0 carried the reacted liquid to the still pot I0. The column I2 and the dephlegmator I3 prevented the polymer that was formed from returning to the catalyst chamber. By adjusting the water ow to the dephlegmators and the steam to the still jacket, the temperature of the stream to the catalyst was kept at C., and the flow of this stream was regulated at 158 pounds per hour. At the end of seven hours of such continuous operation, the polymer was withdrawn from the pot I0 and was found by distillation to contain 9.5 pounds of the dimer, 0.5 pound of an intermediate fraction and 2.3 pounds of the trimer and higher polymers. The yield of the dimer, based upon the pentene-2 consumed, was calculated to be 77%.

Various modications are possible Within the scope of the invention, and I do not therefore wish to be limited except by the scope of the following claim.

I claim:

A continuous process for the dimerization of propylene with the production of tetramethyl ethylene and involving recycling of unpolymerized propylene, comprising continuously vaporizlng propylene from a liquid phase body of said propylene under conditions within 10 C. of but below the critical temperature of said proylene, fractionating the vapors thus produced to separate from said vapors material of higher boiling point than said propylene, thereafter condensing said propylene vapors, flowing the propylene condensate thus produced in a single pass through a bed of activated clay at a rate to maintain the contact time between 1 and 20 seconds and to restrict dimerization of said propylene to less than 10% of the propylene passing through said bed, and Without further contact of the resulting mixture with said activated clay combining said mixture with said original body of propylene for revaporization and recycling of unpolymerized propylene while avoiding recontact of dimer product with said catalyst.

EUGENE V. KLEBER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Gayer, "The Cat. Poly. of Propylene; Ind. and Eng. Chem.. vol. 25, No. 10; Oct.,`1933; pages 1122-1127. ,v 

